JP2006502535A - Method of manufacturing a substantially transparent conductive layer configuration - Google Patents

Abstract

A method for producing a substantially transparent conductive layer configuration on a support, wherein the layer configuration is optionally in any order of formula (I) wherein n is greater than ¹ and each of R ¹ and R ² Each independently represents hydrogen or an optionally substituted C _1-4 alkyl group, or together, optionally substituted C _1-4 alkylene group or optionally substituted. Optionally substituted cycloalkylene group, preferably ethylene group, optionally alkyl-substituted methylene group, optionally C _1-12 alkyl- or phenyl-substituted ethylene group, 1,3- A first layer containing an intrinsically conductive polymer which may contain a structural unit represented by a propylene group or a 1,2-cyclohexylene group] A method comprising the steps of forming a second layer by photographic processing, and a light emitting diode, a photovoltaic device, a transistor and an electroluminescent device produced according to the method. Cent equipment.

Description

  The present invention relates to a method of manufacturing a substantially transparent conductive layer configuration.

  There is a need for an inexpensive transparent conductive layer in many applications, but for some (large area) applications, a busbar will also be required. Highly conductive (non-transparent) patterns can be produced by screen printing conductive pastes such as silver or carbon black paste. Another method is vacuum deposition of metal through a shadow mask. Yet another method uses a uniform conductive metal treated surface that can be patterned by the use of photoresist technology in combination with a metal etchant. Photographic films can also be used for the production of electrically conductive silver “images” under certain conditions.

  U.S. Pat. No. 6,057,089 describes the use of a photosensitive evaporated silver halide film that forms a conductive image upon exposure and after development. U.S. Patent No. 6,057,031 describes a photographic process for making conductive paths, resistors and capacitors for microcircuits starting from coated silver halide emulsions. Patent document 3 describes the production of an electrically conductive pattern by diffusion transfer technology.

  Combinations of transparent polymer based conductors and highly conductive (non-transparent) patterns have been described in several references. Patent Document 4 discloses an electroluminescent configuration containing a hole and / or electron injection layer, and the polymeric organic conductor is selected from the group of polyfuran, polypyrrole, polyaniline, polythiophene and polypyridine. Yes. Patent Document 4 describes the use of poly (3,4-ethylenedioxythiophene) as a charge injection layer on a transparent metal electrode such as ITO (indium tin oxide), and the following substances: a) metal oxide It also discloses that, for example, ITO, tin oxide, etc .; b) translucent metal films, such as Au, Pt, Ag, Cu, etc. are suitable as transparent and conductive materials. The latter is applied by vacuum technology.

  Patent Document 5 discloses an organic electroluminescent device having an anode, an organic hole injecting / transporting layer, an organic fluorescent layer, and a cathode in this order, where the organic hole injecting / transporting layer is made of an aromatic carboxylic acid. Contains metal complexes and / or metal salts. US Pat. No. 6,057,096 further describes different types of conductivity selected from metals such as Al, Au, Ag, Ni, Pd or Te, metal oxides, carbon black or conductive resins such as poly (3-methylthiophene). It is also disclosed that the conductive layer used in such a device by depositing a material can have a multilayer structure, but the specific combination is not illustrated.

  Patent Document 6 discloses a method for producing a pattern of an electrically conductive polymer on a substrate surface, the method comprising: a) a substance capable of generating the electrically conductive polymer on heating on the surface of the substrate; Forming a liquid layer from a solution containing, for example, 3,4-ethylenedioxythiophene, an oxidant and a base, b) exposing the liquid layer to patterned irradiation, and c) heating the layer; Thereby comprising forming a pattern of electrically conductive polymer, the conductive polymer being formed in the unexposed areas of the layer and the nonconductive polymer being formed in the exposed areas. A galvanic provision of a conductive polymer pattern using a metal layer such as silver, copper, nickel or chromium is also disclosed in US Pat.

  Patent Document 7 describes an organic or organometallic electrically conductive polymer in which the first layer is transparent or translucent in the visible range of the electromagnetic spectrum, such as polythiophene, polythiol, polyaniline, polyacetylene or those optionally substituted And the second layer may contain at least one electrically conductive inorganic compound or metal or suitably doped metalloid such as Cu, Ag, Au, Pt, Pd, Fe, Cr, Disclosed is a conductive layer system, particularly for transparent or translucent electrodes or electroluminescent structures, characterized in that it contains a substance selected from the group consisting of Sn, Al or their alloys or conductive carbon Yes. In a preferred embodiment, the second layer is preferably a conductive pattern formed by an open grid structure with a 5-500 μm grid so that it cannot be discerned by the naked eye. Example 2 of the invention is a poly (3,4-ethylenedioxy) having a surface resistance of 1500 Ω / square applied by a printing technique to a conductive track of Leitsilber (silver particle dispersion) about 2 mm wide. A thiophene) [PEDOT] / poly (styrene sulfonate) [PSS] layer is disclosed.

  The layer configuration disclosed in Example 2 of Patent Document 7 requires a thickness of 5-10 μm of a late silver grid to obtain a layer having a surface resistance of 0.5-1 Ω / square, Since the surface of the construction has a certain degree of roughness, its use is limited and has the disadvantage that it makes it difficult to apply a thin, eg 100 nm, functional layer. Furthermore, aqueous PEDOT / PSS dispersions will not wet such late silver grids, and so will not result in a multi-layer conductive configuration that can be used.

In addition, the reverse order of such, the first conductive metal grid and the next conductive transparent polymer layer, will probably be more important in LED devices and thin film photovoltaic devices, There, the transparent polymer electrode functions as a hole injection layer.
US Pat. No. 3,664,837 German Patent No. 1,938,373 US Pat. No. 3,600,185 German Patent Application Publication No. 196 27 071 European Patent Application Publication No. 510 541 US Pat. No. 5,447,824 WO 98/54767 pamphlet

  Accordingly, one aspect of the present invention is a multilayer electrode configuration comprising a conductive polymer layer and a conductive metal layer that can implement either a conductive polymer layer or a conductive metal layer closer to the support. It is to provide a manufacturing method.

  Another aspect of the present invention is to provide a method of manufacturing a multilayer electrode configuration comprising a conductive polymer layer and a conductive metal layer to which a functional layer system can be applied.

  Another aspect of the invention is to prevent ion migration from the conductive electrode.

  Other aspects and advantages of the invention will become apparent from the following description.

SUMMARY OF THE INVENTION By producing a silver grid using photographic processing in a multilayer construction comprising a first layer containing an intrinsically conductive polymer, such as PEDOT / PSS, and a second layer that is a silver pattern, It has surprisingly been found that it is possible to obtain a configuration with a PEDOT / PSS layer or silver pattern on the outermost side and that the functional layer can be easily applied to the outermost layer.

  An aspect of the present invention is a method for producing a substantially transparent conductive layer configuration on a support, the layer configuration comprising a first layer containing an intrinsic conductive polymer and a discontinuous layer of conductive silver The method comprises a second layer in at least any order, and the method is realized by a method comprising the step of producing a second layer by photographic processing.

  An aspect of the present invention is a layer structure obtainable by the method according to the present invention, wherein the layer structure further comprises a 1-phenyl-5-mercapto-tetrazole compound in which the phenyl group is substituted with at least one electron accepting group. It is also realized by the layer structure to be contained.

  Aspects of the present invention are also realized by a light emitting diode comprising a layer structure manufactured according to the above method.

  The aspect of the present invention is also realized by a photovoltaic device comprising a layer structure manufactured according to the above method.

  Aspects of the present invention are also realized by a transistor comprising a layer structure manufactured according to the above method.

  Aspects of the present invention are also realized by an electroluminescent device comprising a layer structure manufactured according to the above method.

Preferred embodiments are disclosed in the dependent claims.
DETAILED DESCRIPTION OF THE INVENTION FIG. 1 shows four silver patterns, namely a pattern (a) representing a continuous silver layer with an area of 3 × 3 cm ² , regular pieces with parallel pieces 10 mm apart and 1 mm width. A pattern (b) representing a pattern, a pattern (c) representing a regular piece pattern with parallel strips separated by 5 mm and having a width of 150 μm, and a pattern (d) representing no silver development are shown.

  FIG. 2 shows the side (upper) and top (bottom) and top of a continuous process for assembling a module with a single photovoltaic cell, two series-connected photovoltaic cells and three series-connected photovoltaic cells using a six-stage method. (Lower) where A = primed support, B = gelatin layer, C = palladium sulfide nucleation layer, D = conductive silver pattern, E = highly conductive PEDOT / PSS-layer, F = shunt resistance blocking layer, G = photovoltaic formulation, and H = lithium fluoride / aluminum electrode. In step 1, the primed surface of the primed poly (ethylene terephthalate) film A [primary layer indicated by thin parallel lines] is coated with gelatin layer B, and in step 2, the palladium sulfide nucleation layer C is gelatinized. Applied to layer B, in step 3, a diffusion transfer process is performed in which a conductive silver pattern D is produced, in step 4, the conductive silver pattern D is formed in a highly conductive PEDOT / PSS-layer, for example by screen printing, and Optionally further coated with a shunt resistance blocking layer F having a higher surface resistance, such as PEDOT / PSS layer or PEDOT-S / polycation or polyanionic polymer, and in step 5, layer E or F is for example curtain coated, spin coated Photocell formulations such as HDMO-P by coating or screen printing Coated with the formulation of the V / PCBM G, and in step 6, the layer G is coated with a non-continuous lithium fluoride / aluminum layer, allowed to form the top electrode H.

Definitions The term alkyl refers to all possible variations for each carbon number in the alkyl group, ie n-propyl and isopropyl for carbon number 3, n-butyl, isobutyl and tertiary-butyl for carbon number 4, Regarding carbon number 5, it means n-pentyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 2-methyl-butyl and the like.

  The term aqueous for the purposes of the present invention includes the inclusion of at least 60% by volume of water, preferably at least 80% by volume of water, and optionally water-miscible organic solvents such as alcohols such as methanol, ethanol, 2 Means the inclusion of propanol, butanol, iso-amyl alcohol, octanol, cetyl alcohol, etc .; glycols such as ethylene glycol; glycerine; N-methylpyrrolidone; methoxypropanol; and ketones such as 2-propanone and 2-butanone To do.

  The term “support” means “self-supporting material” and is distinguished from “layers” which may be coated on the support but which are not themselves self-supporting. It also includes any treatment necessary for adhesion to the support or layers applied to aid it.

  The term continuous layer refers to a layer that covers a whole area of the support and does not necessarily need to be in direct contact with the support.

  The term non-continuous layer refers to a layer where a single surface does not cover the entire area of the support and need not necessarily be in direct contact with the support.

  The term coating refers to all techniques for producing continuous layers, such as curtain coating, doctor-blade coating, etc., and all techniques for producing non-continuous layers, such as screen printing, inkjet printing, flexographic printing, and A generic term that encompasses all means for applying a layer, including techniques for producing a continuous layer.

  The term intrinsically conductive polymer has a (poly) -conjugated π-electron system (eg double bonds, aromatic or heteroaromatic rings or triple bonds) and their conductive properties are eg relative humidity. An organic polymer that is not affected by environmental factors.

The term “conductive” relates to the electrical resistance of a substance. The electrical resistance of the layer is generally indicated by the surface resistance R _S (unit Ω; often expressed as Ω / square). Alternatively, the conductivity is volume resistivity R _v = R _S · d (where d is the thickness of the layer), volume conductivity k _V = 1 / R _v [unit: S (iemens) / cm] or surface Conductance k _S = 1 / R _S [unit: S (iemens). Square] can also be used.

  The term photography refers to any photochemical method, in particular based on the silver halide method.

  The term silver salt diffusion transfer method refers to A. Rott [British Patent No. 614,155 and Sci. Photogr. , (2) 13, 151 (1942)] and E.I. Developed independently by Weyde [DE 973,769] and G.W. I. P. “The Theory of the Photographic Process Fourth Edition” edited by T. Levenson. H. Refers to the method described in James, pages 466 to 480, Eastman Kodak Company, Rochester (1977).

  The term substantially transparent means that the integral transmission of visible light is above 40% of the standard incident light in the layer construction of the present invention, i.e. the layer has an overall optical power lower than 0.40. The local transmission of visible light that had a density but through the lines of the silver pattern may be well below 10% of the standard incident light in the layer configuration of the invention, ie an optical density of 1.0 Means it may be much higher.

  The abbreviation PEDOT stands for poly (3,4-ethylenedioxy-thiophene).

  The abbreviation PSS stands for poly (styrene sulfonic acid) or poly (styrene sulfonate).

  The abbreviation PEDOT-S represents poly [4- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-ylmethoxy) -butane-1-sulfonic acid].

A method for producing a layer structure An aspect of the present invention is a method for producing a substantially transparent conductive layer structure on a support, wherein the layer structure comprises a first layer containing an intrinsically conductive polymer and conductive silver. The method comprises a second layer comprising a non-continuous layer in at least any order, and this method is realized by a method comprising the step of producing a second layer by photographic processing.

  According to a first embodiment of the method according to the invention, the method further comprises coating the first layer before producing the second layer by photographic processing.

  According to a second embodiment of the method according to the invention, the photographic processing is performed by coating the support with a layer containing silver halide and gelatin in a weight ratio of gelatin to silver halide in the range of 0.05 to 0.3. Exposing the silver halide-containing layer imagewise and developing the exposed silver halide-containing layer to produce a second layer.

  According to a third embodiment of the method according to the invention, the method coats the support with a first layer, the first layer comprising silver halide and gelatin in the range of 0.05 to 0.3. Coating with a layer containing a silver halide weight ratio, exposing the silver halide-containing layer image-wise, and developing the exposed silver halide-containing layer to produce a second layer. Comprising.

  According to a fourth embodiment of the method according to the invention, the method comprises coating the support with a layer containing silver halide and gelatin in a weight ratio of gelatin to silver halide in the range of 0.05 to 0.3. Coating the silver halide-containing layer with the first layer, exposing the silver halide-containing layer imagewise, and developing the exposed silver halide-containing layer to produce a second layer Comprising steps.

  According to a fifth embodiment of the method according to the invention, the method comprises coating the support with a layer containing silver halide and gelatin in a weight ratio of gelatin to silver halide in the range of 0.05 to 0.3. Imagewise exposing the silver halide-containing layer, developing the exposed silver halide-containing layer to produce a second layer, and coating the second layer with the first layer. Comprising.

  According to a sixth embodiment of the method according to the present invention, the photographic processing comprises coating the support with a discontinuous layer of nucleation agent and applying a second layer on the discontinuous nucleation layer using silver salt diffusion transfer. Comprising the step of manufacturing.

  According to a seventh aspect of the method according to the present invention, the photographic processing comprises coating the support with a first layer, coating the first layer with a layer of nucleating agent, and using silver salt diffusion transfer to form the nucleation layer. Producing a discontinuous silver layer thereon.

  According to an eighth embodiment of the method according to the present invention, the photographic processing comprises coating the support with a discontinuous layer of nucleation agent, coating the discontinuous layer of nucleation agent with a first layer, and silver salt diffusion transfer. To produce a discontinuous silver layer on the discontinuous nucleation layer.

  According to a ninth aspect of the method according to the invention, the photographic processing is carried out by coating the support with a discontinuous layer of palladium sulfide as a nucleating agent, for example palladium sulfide nanoparticles, and discontinuous using silver salt diffusion transfer. Producing a discontinuous silver layer on the active nucleation layer.

  According to a tenth aspect of the method according to the present invention, the method coats the support with a discontinuous layer of nucleation agent and uses silver salt diffusion transfer to form a second layer on the discontinuous nucleation layer. Manufacturing and coating the second layer with the first layer.

  According to an eleventh aspect of the method according to the invention, the first layer is applied by a printing method.

Intrinsically Conducting Polymer The intrinsically conducting polymer used in the present invention can be any intrinsically conducting polymer known in the art, such as polyacetylene, polypyrrole, polyaniline, polythiophene, and the like. Details of suitable intrinsic conducting polymers can be found in, for example, “Advanceds in Synthetic Metals”, ed. P. Bernier, S.M. Lefrant, and G.L. Bidan, Elsevier, 1999; “Intrinsically Conducting Polymers: An Emerging Technology”, Kluwer (1993); “Conducting Polymer Funding Funds and Amplifications”. Chandrasekhar, Kluwer, 1999; and “Handbook of Organic Conducting Molecules and Polymers”, Ed. Walwa, Vol. 1-4, Marcel Dekker Inc. It can be seen in textbooks such as (1997).

  According to a twelfth aspect of the method according to the invention, the intrinsically conductive polymer is of formula (I):

[Wherein each of R ¹ and R ² independently represents hydrogen or a C _1-4 alkyl group, or together represents an optionally substituted C _1-4 alkylene group or cycloalkylene group. Represent]
The structural unit shown by is contained.

  According to a thirteenth embodiment of the process according to the invention, the intrinsically conductive polymer is a 3,4-dioxy group representing an oxy-alkylene-oxy bridge in which two alkoxy groups are optionally substituted. It is a polymer or copolymer of alkoxythiophene.

  According to a fourteenth embodiment of the process according to the invention, the intrinsically conductive polymer represents an oxy-alkylene-oxy bridge in which two alkoxy groups are optionally substituted together and is poly (3, 4-methylenedioxythiophene), poly (3,4-methylenedioxythiophene) derivative, poly (3,4-ethylenedioxythiophene), poly (3,4-ethylene-dioxythiophene) derivative, poly (3 , 4-propylenedioxy-thiophene), poly (3,4-propylenedioxy-thiophene) derivatives, poly (3,4-butylene-dioxythiophene) and poly (3,4-butylenedioxy-thiophene) derivatives , As well as 3,4-dialkoxythiophene polymers or copolymers thereof.

  According to a fifteenth embodiment of the process according to the invention, the intrinsically conductive polymer represents an oxy-alkylene-oxy bridge in which two alkoxy groups are optionally substituted together and represents an oxy-alkylene- Polymers or copolymers of 3,4-dialkoxythiophene where the substituents on the oxy bridge are alkyl, alkoxy, alkyloxyalkyl, carboxy, alkyl sulfonate and carboxy ester groups.

  According to a sixteenth embodiment of the process according to the invention, the intrinsically conductive polymer represents an oxy-alkylene-oxy bridge in which two alkoxy groups are optionally substituted together and two alkoxy groups. The groups taken together are 1,2-ethylene groups, optionally alkyl-substituted methylene groups, optionally C1-12 alkyl- or phenyl-substituted 1,2-ethylene groups, 1 1,4-propylene group or 1,2-cyclohexylene group, a polymer or copolymer of 3,4-dialkoxythiophene representing an optionally substituted oxy-alkylene-oxy bridge.

  Such polymers are available from Handbook of Oligo- and Polythiophenes Edited by D.D. Fichu, Wiley-VCH, Weinheim (1999); Groendaal et al. in Advanced Materials, volume 12, pages 481-494 (2000); J. et al. Kloepner et al. in Polymer Preprints, volume 40 (2), page 792 (1999); Schottland et al. in Synthetic Metals, volume 101, pages 7-8 (1999); M.M. Welsh et al. in Polymer Preprints, volume 38 (2), page 320 (1997).

Organic polymers containing structural units according to formula (I) can be polymerized chemically or electrochemically. Chemical polymerization can be carried out oxidatively or reductively. For example, J. et al. Amer. Chem. Soc. , Vol. 85, pages 454-458 (1963) and J.A. Polym. Sci. Part A Polymer Chemistry, vol. 26, pages 1287-1294 (1988), oxidizing agents used for the oxidative polymerization of pyrrole can be used for the oxidative polymerization of thiophenes. According to the seventeenth aspect of the present invention, an inexpensive and readily available oxidant, such as an iron (III) salt, such as FeCl ₃ , an iron (III) salt of an organic acid, such as Fe (OTs) ₃ , H ₂ O ₂ , K ₂ Cr ₂ O ₇ , alkali and ammonium persulfates, alkali perborates and potassium permanganate are used in the oxidative polymerization.

  Theoretically, oxidative polymerization of thiophenes requires 2.25 equivalents of oxidizing agent per mole of thiophene of formula (I) [see, for example, J. Org. Polym. Sci. Part A Polym. Chem. , Vol. 26, pages 1287-1294 (1988)]. In practice, an excess of 0.1 to 2 equivalents of oxidizing agent is used per polymerizable unit. The use of persulfates and iron (III) salts has the great technical advantage that they do not corrode. Furthermore, in the presence of certain additives, the oxidative polymerization of thiophene compounds according to formula (I) proceeds very slowly, so that thiophenes and oxidants are combined in solution or paste and applied to the substrate to be treated. can do. For example, after application of such a solution or paste, as disclosed in US Pat. No. 6,001,281 and International Publication No. 00/14139, which are incorporated herein by reference. Oxidative polymerization can be accelerated by heating the coated substrate.

  Reductive polymerization was performed in Appperloo et al. Chem. Eur. Journal, volume 8, pages 2384-2396 and disclosed in 2001 in Tetrahedron Letters, volume 42, pages 155-157 and in 1998 in Macromolecules, volume 31, pages 2047-2056 ) Or the Suzuki (organoboron) process or in 1999 in Bull. Chem. Soc. Japan, volume 72, page 621, and nickel complexes disclosed in 1998 in Advanced Materials, volume 10, pages 93-116.

1-phenyl-5-mercapto-tetrazole compound substituted with at least one electron-accepting group Aspects of the present invention are directed to 1-phenyl having a phenyl group substituted with at least one electron-accepting group. It is also realized by the layer structure obtainable by the method according to the invention which further contains a -5-mercapto-tetrazole compound.

  According to a first embodiment of the layered conductive layer obtainable by the method according to the invention, the electron accepting group is selected from the group consisting of chloride, fluoride, cyano, sulfonyl, nitro, acid amide and acylamino groups.

  According to a second embodiment of the layer-structured conductive layer obtainable by the method according to the invention, 1-phenyl-5-mercapto-tetrazole compound in which the phenyl group is substituted with at least one electron accepting group is 1- (3 ', 4'-dichlorophenyl) -5-mercapto-tetrazole,

Selected from the group consisting of:

  Suitable 1-phenyl-5-mercapto-tetrazole compounds [PMT] having a substituted phenyl group according to the present invention include:

Printing Ink Containing Intrinsically Conducting Polymer According to the seventeenth aspect of the method according to the invention, the first layer is applied by a printing method using an ink or paste containing the intrinsic conducting polymer.

  2,4-dioxy represents an oxy-alkylene-oxy bridge in which between 0.08 and 3.0% by weight of two alkoxy may be the same or different or together may be optionally substituted. A printing ink or paste containing a polymer or copolymer of alkoxythiophene, a polyanion and a non-aqueous solvent is obtained from an aqueous dispersion of a polymer or copolymer of (3,4-dialkoxythiophene) and a polyanion i) At least one non-aqueous solvent is mixed with an aqueous dispersion of a polymer or copolymer of (3,4-dialkoxythiophene) and a polyanion, and ii) water is contained therein from the mixture prepared in step i). Can be produced by a process comprising the step of evaporating until the water content is reduced by at least 65% by weight.

Surfactant According to a third embodiment of the layer configuration according to the invention, the layer configuration further comprises a surfactant.

  According to a fourth embodiment of the layer composition according to the invention, the layer composition comprises a nonionic surfactant, such as an ethoxylated / fluoro-alkyl surfactant, a polyethoxylated silicone surfactant, a polysiloxane / polysiloxane. It further comprises an ether surfactant, an ammonium salt of a perfluoro-alkyl carboxylic acid, a polyethoxylated surfactant and a fluorine-containing surfactant.

Suitable nonionic surfactants include the following:
Surfactant number 01 = ZONYL ^™ FSN from DuPont, F (CF ₂ CF ₂ ) _1-9 CH ₂ CH ₂ O (CH ₂ CH ₂ O) in a 50 wt% solution of isopropanol in water _x H [wherein, x = 0 to about 25] 40 wt% solution of;
Surfactant number 02 = Zonyl ^™ FSN-100 from DuPont: F (CF ₂ CF ₂ ) _1-9 CH ₂ CH ₂ O (CH ₂ CH ₂ O) _x H, where x = 0 to about 25 is there];
Surfactant No. 03 = Zonyl ^TM FS300 from DuPont, 40 wt% aqueous solution of fluorinated surfactant;
Surfactant No. 04 = Zonyl ^™ FSO from DuPont, Formula F (CF ₂ CF ₂ ) _1-7 CH ₂ CH ₂ O (CH ₂ CH ₂ O) _y H in a 50 wt% solution of ethylene glycol in water [Formula In which y = 0 to about 15] a 50 wt% solution of a mixture of ethoxylated nonionic fluoro-surfactants;
Surfactant No. 05 = Zonyl ^TM FSO-100 from DuPont, Formula F (CF ₂ CF ₂ ) _1-7 CH ₂ CH ₂ O (CH ₂ CH ₂ O) _y H [where y = 0 to about 15 A mixture of ethoxylated nonionic fluoro-surfactants from DuPont with
Surfactant No. 06 = Tegoglide ^™ 410 from Goldschmidt, polysiloxane-polymer copolymer surfactant;
Surfactant No. 07 = Tegowet ^™ from Goldschmidt, polysiloxane-polyester copolymer surfactant;
Surfactant Nr 08 = Fluorad from _{^{3M (FLUORAD) TM FC431: CF}} 3 (CF 2) 7 SO 2 (C 2 H 5) N-CH 2 CO- (OCH 2 CH 2) n OH;
Surfactant number 09 = Fluorad ^™ FC126 from 3M, mixture of ammonium salts of perfluorocarboxylic acid;
Surfactant No. 10 = Polyoxyethylene-10-lauryl ether Surfactant No. 11 = Fluorad ^™ FC430 from 3M, 98.5% active fluoroaliphatic ester;
According to a fifth aspect of the layer configuration according to the invention, the layer configuration further comprises an anionic surfactant.

Suitable anionic surfactants include the following:
Surfactant No. 12 = Zonyl ^TM 7950 from DuPont, fluorinated surfactant;
Surfactant No. 13 = Zonyl ^™ FSA from DuPont, F (CF ₂ CF ₂ ) _1-9 CH ₂ CH ₂ SCH ₂ CH ₂ COOLi in a 50 wt% solution of isopropanol in water;
Surfactant No. 14 = Zonyl ^TM FSE from DuPont, [F (CF ₂ CF ₂ ) _1-7 CH ₂ CH ₂ O] _x P (O) (ONH ₄ ) _y in 70 wt% aqueous ethylene glycol solution In which x = 1 or 2, y = 2 or 1, and x + y = 3];
Surfactant No. 15 = Zonyl ^TM FSJ from DuPont, F (CF ₂ CF ₂ ) _1-7 CH ₂ CH ₂ O] _x P (O) (ONH ₄ ) _{y in a} 25 wt% solution of isopropanol in water In which x = 1 or 2, y = 2 or 1, and x + y = 3] and a 40% by weight solution of a blend of hydrocarbon surfactants;
Surfactant No. 16 = Zonyl ^™ FSP from DuPont, [F (CF ₂ CF ₂ ) _1-7 CH ₂ CH ₂ O] _x P (O) (ONH ₄ ) in a 69.2 wt% solution of isopropanol in water _y [wherein a x = 1 or 2, y = 2 or 1, and x + y = 3 is a] 35 wt% solution of;
Surfactant number 17 = Zonyl ^TM UR from DuPont: [F (CF ₂ CF ₂ ) _1-7 CH ₂ CH ₂ O] _x P (O) (OH) _y [wherein x = 1 or 2 Y = 2 or 1 and x + y = 3];
Surfactant No. 18 = Zonyl ^™ TBS from DuPont, 33 wt% solution of F (CF ₂ CF ₂ ) _3-8 CH ₂ CH ₂ SO ₃ H in 4.5 wt% solution of acetic acid in water;
Surfactant No. 19 = Perfluoro-octanoic acid ammonium salt from 3M
Binder According to a sixth embodiment of the layer configuration according to the invention, the layer configuration further comprises a binder.

Crosslinking agent According to a seventh embodiment of the layer configuration according to the invention, the layer configuration further comprises a crosslinking agent.

Electroluminescent phosphor According to an eighth aspect of the layer configuration according to the invention, the layer configuration further comprises a layer of electroluminescent phosphor.

  According to a ninth aspect of the layer arrangement according to the invention, the layer configuration further comprises a layer of an electroluminescent phosphor, wherein the electroluminescent phosphor belongs to a group II-VI semiconductor, for example ZnS. Or a combination of Group II elements and oxidizing anions, with silicates, phosphates, carbonates, germanates, stannates, borates, vanadates, tungstates and oxysulfates being the most universal Is. Typical dopants are metals and all rare earths such as Cu, Ag, Mn, Eu, Sm, Tb and Ce.

According to a tenth aspect of the layer arrangement according to the invention, the layer arrangement further comprises a layer of electroluminescent phosphor, wherein the electroluminescent phosphor comprises a transparent moisture barrier layer, for example Al ₂ O ₃ and Encapsulated with AlN. Such phosphors are available from Sylvania, Shinetsu Polymer KK, Dural, Acheson, and Toshiba. Examples of coatings using such phosphors are the 72X available from Sylvania / GTE and the coating disclosed in US Pat. No. 4,855,189.

According to an eleventh aspect of the layer arrangement according to the invention, the layer arrangement further comprises a layer of electroluminescent phosphor, wherein the electroluminescent phosphor is ZnS doped with manganese, copper or terbium or CaGa ₂ S ₄ doped with cerium, eg electroluminescent phosphor paste supplied by DuPont: LUXPRINT ^TM type 7138J which is a white phosphor; Lux Print ^TM type which is a green-blue phosphor 7151J; and Luxprint ^™ Type 7174J, which is a yellow-green phosphor; and ELECTRODAG ^™ EL-035A supplied by Acheson.

  According to a twelfth embodiment of the layer arrangement according to the invention, the layer configuration further comprises a layer of electroluminescent phosphor, wherein the electroluminescent phosphor is doped with manganese and encapsulated with AlN. Zinc sulfide phosphor.

Dielectric Layer According to a thirteenth aspect of the layer configuration according to the present invention, the layer configuration further includes a dielectric layer.

Any dielectric material can be used in the dielectric layer, such as yttria titanate and barium, for example Luxprint ^TM type 7153E high-K dielectric insulator supplied by DuPont and titanium supplied by Acheson. Electrodag ^TM EL-040, which is a barium acid paste, is preferred. A positive ion exchanger can be added in the dielectric layer to trap soluble ions that escape from the phosphor in the luminescent layer. The amount of exchanger in the dielectric layer should be optimized so that it does not reduce the initial brightness level while having the greatest effect on sunspot reduction. Therefore, it is preferable to add 0.5 to 50 parts by weight of the ion exchanger to 100 parts by weight of the total amount of resin and dielectric material in the dielectric layer. The ion exchanger can be organic or inorganic.

  Suitable inorganic ion exchangers are hydrated antimony pentoxide powder, titanium phosphate, phosphoric acid and silicic acid salts, and zeolites.

Support According to a fourteenth aspect of the layer configuration according to the present invention, the support is transparent or translucent.

  According to a fifteenth aspect of the layer configuration according to the invention, the support is polymer film, silicon, ceramic, oxide, glass, polymer film tempered glass, glass / plastic laminate, metal / plastic laminate, optionally treated. Paper and laminated paper that may be included.

  According to a sixteenth aspect of the layer configuration according to the present invention, the support is provided with other adhesion promoting means to help adhere to the subbing layer or the substantially transparent layer configuration.

  According to a seventeenth aspect of the layer configuration according to the invention, the support is a transparent or translucent polymer film.

  Transparent or translucent supports suitable for use with the electrically conductive layer or antistatic layer according to the present invention may be hard or soft and glass, glass-polymer laminates, polymer laminates, thermoplastic polymers Alternatively, it can be made of a juroplastic polymer. Examples of thin flexible supports are cellulose esters, cellulose triacetates, polypropylene, polycarbonates or polyesters, poly (ethylene terephthalate), optionally treated by corona discharge or glow discharge or provided with a subbing layer , Poly (ethylene naphthalene-1,4-dicarboxylate), polystyrene, polyethersulfone, polycarbonate, polyacrylate, polyamide, polyimides, cellulose triacetate, polyolefins and poly (vinyl chloride). .

Electroluminescent Device The features of the present invention are realized by an electroluminescent device according to the present invention comprising a layer structure manufactured according to the present invention.

  According to an eighteenth aspect of the layer configuration according to the invention, the layer configuration is an electroluminescent device.

  According to a nineteenth aspect of the layer configuration according to the invention, the layer configuration is a light emitting diode.

  Thin film electroluminescent devices (ELDs) are all characterized by one (or more) electroluminescent active layers sandwiched between two electrodes. In some cases, the dielectric layer may be part of a sandwich.

  Thin film ELDs can be subdivided into organic and inorganic based ELDs. Organic-based thin film ELDs can be subdivided into low molecular weight organic devices (organic light emitting diode (OLED)) and oligomeric organic devices (polymer light emitting diode (PLED)), including oligomers. On the other hand, inorganic ELDs can be further subdivided into high voltage alternating current (HV-AC) ELD and low voltage direct current (LV-DC) ELD. LV-DC ELDs include powder ELDs (DC-PEL devices or DC-PELD) and thin film DCC-ELDs, hereinafter referred to as inorganic light emitting diodes (ILEDs).

  The basic structure of an organic ELD (PLED and OLED) comprises the following layer arrangement: a transparent substrate (glass or soft plastic), a transparent conductor such as indium tin oxide (ITO), a hole transport layer, fluorescence Layer, and a second electrode, such as a Ca, Mg / Ag or Al / Li electrode. For OLEDs, the hole transport and phosphor layers are 10-50 nm thick and are applied by vacuum deposition, whereas for PLEDs, the hole transport layer is typically about 40 nm thick and the phosphor layer is typically about 100 nm thick. And applied by spin coating or other non-vacuum coating techniques. An energy for applying a DC voltage of 5-10 V between the electrodes and emitting light from the holes and injecting electrons from the positive and negative electrodes, respectively, to combine in the fluorescent layer and thereby excite the fluorescent species. To emit light.

  In the OLED, the hole transport layer and the electroluminescent layer are made of a low molecular weight organic compound, and for example, N, N′-diphenyl-1,1′-biphenyl-4,4′-diamine is used as the hole transporter. And aluminum (III) 8-hydroxyquinoline complexes, polyaromatics (anthracene, perylene and stilbene derivatives) and polyheteroaromatics (oxazole, oxadiazole, thiazole, etc.) can be used as electroluminescent devices it can. For PLEDs, the electroluminescent compounds that can be used are polymers such as non-conjugated poly (N-vinylcarbazole) derivatives (PVK) or poly (p-phenylene vinylene) (PPV), polyfluorene, poly (3-alkylthiophene). And conjugated polymers such as poly (p-phenyleneethynylene).

  A low voltage DC PEL device typically comprises a transparent substrate, a transparent conductor (ITO), a doped ZnS phosphor layer (20 μm), and a top electrode of evaporated aluminum. The phosphor layer is applied by evaporation onto the ITO conductive layer by doctor blade technology or screen printing technology. When a direct voltage of several volts (ITO positive) is applied, the holes move toward the aluminum electrode, thereby creating an insulating region (thickness about 1 μm) next to the ITO layer within about 1 minute. This results in a current drop that is associated with the onset of light emission. This method has been referred to as the forming process. In the thin high-resistance phosphor layer formed thereby, a high electric field is generated and electroluminescence can already occur at low voltages (typically between 10-30V).

  In hybrid LEDs, so-called quantum short spots with inorganic luminescence are used in combination with organic polymers having charge transport properties and in some cases luminescent properties. Hybrid LEDs with CdSe nanoparticles are described in Colvin et al., Which is incorporated herein by reference. [See Nature, volume 370, pages 354-357, (1994)], Dabbousi et al. [Appl. Phys. Lett. , Volume 66, pages 1316-1318 (1995)], and Gao et al. [J. Phys. Chem. B, volume 102, pages 4096-4103 (1998)].

  A light-emitting device having ZnS: Cu nanocrystals and a non-conducting polymer operating at a voltage lower than 5 V is disclosed in Huang et al., Which is incorporated herein by reference. [Appl. Phys. Lett. , Volume 70, pages 2335-2337 (1997)] and Que et al. Appl. Phys. Lett. , Volume 73, pages 2727-2729 [1998]].

Photovoltaic Device Aspects of the present invention are realized by a photovoltaic device according to the present invention comprising a layer configuration produced according to the present invention.

  According to a twentieth aspect of the layer configuration according to the present invention, the layer configuration is a photovoltaic device.

  According to a twenty-first aspect of the layer configuration according to the invention, the layer configuration further comprises at least one photovoltaic cell layer. The photovoltaic layer can be an organic layer, a hybrid inorganic and organic layer or an inorganic layer.

  According to a twenty-second aspect of the layer configuration according to the invention, the layer configuration is a solar cell.

  Photovoltaic devices incorporating the layer structure according to the present invention are of two types: current carrying electrons are transferred to the anode and external circuits and holes are transferred to the cathode without converting the light into electrical power and leaving a substantial chemical change. Regenerative types where they are oxidized by electrons from the external circuit, as well as one reacts with holes on the surface of the semiconductor electrode and one with electrons entering the reverse electrode, eg water is oxidized at the semiconductor photoanode and There may be a photosynthetic type with two redox systems that are reduced to hydrogen at the cathode. In the case of the photovoltaic cell regeneration type exemplified by the Graetzel cell, the electron transport medium is a nanoporous metal oxide semiconductor having a band-gap greater than 2.9 eV, such as titanium dioxide, niobium oxide (V ), Tantalum (V) oxide and zinc oxide, the hole transport medium being a liquid electrolyte that aids the redox reaction, a gel electrolyte that aids the redox reaction, a low molecular weight material such as 2,2 ′, 7,7′- Tetrakis (N, N-di-p-methoxyphenyl-amine) 9,9'-spirobifluorene (OMeTAD) or triphenylamine compounds or polymers such as PPV derivatives, poly (N-vinylcarbazole), etc. Organic hole transport material or inorganic semiconductor such as CuI, CuSCN, etc. That. The charge transfer method can be ionic as in the case of liquid or gel electrolytes, or it can be electronic as in the case of organic or inorganic hole transport materials.

  Such a regenerative photovoltaic cell device can have various internal structures according to the end use. The possible forms are roughly classified into two types: structures that receive light from both sides and those that receive light from one side. Examples of the former are transparent conductive layers, such as ITO-layers or PEDOT / PSS-containing layers and transparent reverse electrode electrically conductive layers, such as ITO-layers or PEDOTs having a sandwiched photosensitive layer and charge transport layer This is a structure manufactured from a / PSS-containing layer. Such devices preferably have their sides sealed with polymers, adhesives, etc. to prevent degradation or volatilization of internal materials. External circuits connected to the electrically conductive substrate and the counter electrode by respective conductors are known.

Alternatively, a spectrally sensitized nano-porous metal oxide according to the present invention was prepared in 1991 by Graetzel et al. In Nature, volume 353, pages 737-740, U.S.A. in 1998. Bach et al. [See Nature, volume 395, pages 83-585 (1998)], and in 2002. U. Huynh et al. [See Science, volume 295, pages 2425-2427 (2002)]. In all these cases, at least one of the components (light absorber, electron transfer agent or hole transfer agent) is inorganic (eg nano-TiO ₂ as electron transfer agent, light absorber and electron transfer agent) And at least one of the components is organic (eg, triphenylamine as a hole transfer agent or poly (3-hexylthiophene) as a hole transfer agent).

Transistors Aspects of the present invention are realized by a transistor according to the present invention comprising a layer structure manufactured according to the present invention.

  According to the twenty-third aspect of the layer configuration according to the present invention, the layer configuration further comprises a layer having one or more of the electron transport or hole transport components described above, which can be used as a transistor. Comprising in. The semiconductor can be n-type, p-type or both (ambipolar transistors) and can be either organic or inorganic.

Industrial applications A layer configuration comprising at least a first layer comprising an intrinsically conductive polymer and a second layer comprising a discontinuous layer of conductive silver comprises a wide range of electronic devices such as photovoltaic devices, solar cells, Can be used in batteries, capacitors, light emitting diodes, organic and inorganic electroluminescent devices, smart windows, electrochromic devices, sensors for organic and bioorganic materials and field effect transistors [Handbook of Oligo- and Polythiophenes, Edited by D. See also Chapter 10 of Fichu, Wiley-VCH, Heinheim (1999)].

  The invention is illustrated by the examples below. The percentages and ratios indicated in these examples are by weight unless otherwise indicated.

  Ingredients used in the comparative experiment of Example 2:

Example 1
Preparation of a conductive Ag-pattern photographic emulsion layer prepared by development of a silver halide emulsion having an outermost PEDOT / PSS layer:
Photographic AgCl (63.29%) Br (36.31%) I (0.40%) emulsion in gelatin was prepared using a double jet precipitation technique. The average silver halide grain size was 300 nm. After the precipitation stage, the emulsion was washed and various amounts of gelatin were added to produce the gelatin to AgNO ₃ (g / g) ratio listed in Table 1. The emulsion was chemically ripened and spectrally sensitized to make the emulsion sensitive to He / Ne laser exposure. The emulsion was coated on a primed 100 μm thick polyethylene terephthalate support to a coverage corresponding to 5 g AgNO ₃ per square meter. This is photographic material A.
Surface resistance measurement:
Surface resistance measurements were performed as follows: the layer electrode configuration can be cut into 3.5 cm wide pieces to ensure complete placement of the electrode material, line contact can be produced, and TEFLON The contact area of 3.5 × 3.5 cm ² is obtained by bringing parallel copper electrodes, each 35 mm long and 3 mm wide and 35 mm apart, placed on the ^TM insulator into contact with the outermost conductive layer of the piece. A constant contact force was ensured by placing a 4 kg weight on a Teflon ^™ platform, and the surface resistance was then measured directly using a Fluke-77III multimeter.

AGFA-GEVAERT ^™ All-field exposure using an AVANTRA recorder and subsequent development in Agfa-Gebert ^™ IPD plus developer, fixing in Agfa-Gebert ^™ G333 fixer Table 1 shows the surface resistance measured for various gelatin to AgNO ₃ ratios after and last rinse in water.

Table 1 shows that the lower the gelatin content, the lower the surface resistance. This can be explained by the developed silver particles that are in contact with each other at low gelatin content and as a result create a conduction path. Although material A5 yields the highest surface conductance, material A4 was used in subsequent examples for reasons of simplicity.
Production of PEDOT / PSS dispersions EP 686,62 (US Pat. No. 5,766,515) discloses the production of 1.2% PEDOT / PSS in water dispersions in the examples. ing. 15 mL Zonyl ^™ FSO100 2% aqueous solution, 1.25 g Z6040 silane from Dow CORNING and 25 g diethylene glycol are added to 106 g of this dispersion and PEDOT / PSS used in the following examples A dispersion was given.
Production of a double layer electrode configuration of material B:
The unexposed material A4 was coated with a PEDOT / PSS dispersion to a wet thickness of 50 μm and then dried at 120 ° C. for 20 minutes. The surface resistance of the PEDOT / PSS layer was about 500 Ω / square. The resulting layer structure was then exposed on an Agfa-Gebert ^™ Avantola recorder having the pattern shown in FIG. 1 and developed as described above.
Production of double-layer electrode configuration of material C:
PEDOT / PSS-dispersion was coated on treated material A4 to a wet thickness of 50 μm and then dried at 120 ° C. for 20 minutes, thereby producing material C. The surface resistance of the PEDOT / PSS layer was about 500 Ω / square for the unexposed region material A4.
Evaluation of materials A4 (exposed and developed), B and C:
The surface resistance measured as described above for the double layer electrode configuration with the developed silver pattern coated with the PEDOT / PSS outermost layer of materials B and C was measured with the PEDOT / PSS outermost layer as a control material. Table 2 along with those for the unexposed and developed material A4.

The optical density of the layer structure is the pattern type (d) in which silver was not developed and the pattern type in which silver was developed over the entire area of 3 cm × 3 cm without subtracting the density of the support for the layer structure without photographic processing ( In a), the transmittance was measured using a MacBeth ^™ TD924 densitometer with a visible filter. These measurements were then used to calculate the total optical density for patterns (b) and (c). The optical density results are also shown in Table 2.

  From Table 2, it can be seen that (1) the PEDOT / PSS layer can be exposed to IPD plus developer and G333 fixer with only a small loss in surface conductivity, and (2) the Ag-line is “apparent” surface conductivity. It can be concluded that the rate is increased. Depending on the measurement settings, only PEDOT / PSS is in contact (top layer). From the high surface conductivity values, the PEDOT / PSS-Ag contact appears to be resistive.

  If the PEDOT / PSS coating is applied prior to exposure and development, it functions as a protective coating and as a result, material B is in most cases preferred over material C because of the risk of material damage This is because automatic processing (exposure and development) can be performed without any property.

Example 2
Production of material D, a conductive Ag-pattern control material produced by DTR with conductive PEDOT / PSS on top:
The production of physical development nuclei (PdS) is described in the examples of EP 0 769 723. From this example, nuclei were prepared using solutions A1, B1 and C1. To 1000 mL of this PdS dispersion, 10 g of an Aerosol ^™ OT 10 g / L aqueous solution from American Cyanamid and 5 g of a 50 g / L aqueous solution of perfluorocaprylamide-polyglycol were added. This dispersion was then coated onto a poly (ethylene terephthalate) support having a 4 μm thick gelatin subbing layer to a wet layer thickness of 13.5 μm and then dried at 25 ° C. for 60 minutes. This is material D.
Production of material E:
Material D was coated to a wet thickness of 40 μm using the PEDOT / PSS dispersion described above and then dried at 100 ° C. for 15 minutes, thereby producing Material E.
Production of transfer emulsion layer:
Manufacturing production and transfer emulsion layer chloro silver bromide emulsion, except that the coverage of the applied silver halide corresponded to AgNO ₃ of 1.25 g / ^{m 2} in place of 2 g / ^{m 2,} the European Patent This was as disclosed in Japanese Patent Application No. 769723.
Exposure and development of materials D and E:
The transferred emulsion layer is image-wise exposed as shown in FIG. 1 and processed with Agfa-Gebert ^TM CP297 developer solution at 25 ° C. for 10 seconds in contact with the receiver (Material D and Material E). did.
Manufacture of double layer electrode configuration:
The treated material D was coated with the above PEDOT / PSS-dispersion to a wet layer thickness of 50 μm and then dried at 120 ° C. for 20 minutes. The surface resistance of the PEDOT / PSS layer was about 500 ohms / square in the unexposed areas of Material D. Material F was thereby produced.
Evaluation of materials D, E and F:
Table 3 shows the surface resistance and optical density (finished material) after exposure and development according to the pattern shown in FIG.

From Table 3, (1) transferring the Ag-salt through the PEDOT / PSS layer, (2) aggregating the PEDOT / PSS layer with only a small loss in surface conductivity without affecting the optical transparency. It can be concluded that exposure to ^TM CP297 developer and (3) Ag-line can significantly increase the “apparent” surface conductivity.

Only the outermost PEDOT / PSS layer is contacted during the surface resistance measurement. From the high surface conductivity values, the PEDOT / PSS-Ag contact appears to be resistive. If the PEDOT / PSS coating is applied prior to exposure and development, it functions as a protective coating and as a result material E is preferred over material F in most cases because there is no risk of material damage This is because automatic processing (exposure and development) becomes possible.
Improvement of surface conductance of Ag ⁰ -image after corrosion and chemical development in the presence of halide ions Due to the fact that the DTR method is physical development, the resulting Ag ⁰ -particles are smooth and round. The more dangerous chemical development will result in higher particle overlap and particle contact and as a result a pattern with higher conductivity. However, this type of development does not occur in the DTR process. Ag obtained according to the DTR method 0 ^- to improve the surface conductance of the statue, conductive Ag 0 obtained by the DTR-process ^- a pattern initially it was treated with a corrosion solution containing an oxidizing agent and a halide ion (which by the Ag ⁰ by halide used AgCl, partially oxidized to Ag ⁺ which is present as AgBr or AgBrCl), then results in the newly formed hazardous i.e. chemical development of silver halide graphic developer ( Further processing is carried out by developing with a graphical developer and finally fixing and washing. When this method is applied to a newly produced processed material D having an “a” pattern using Agfa-Gebert ^™ IPD Plus developer and Agfa-Gebert ^™ G333 fixer, 18% in surface resistance. Reduction (= 18% increase in surface conductance) was obtained. The corrosion bath composition and corrosion time are shown in Table 4.

The optical density was measured using a Macbeth ^TM densitometer with a visible filter. The obtained surface resistance and optical density are shown in Table 5.

  From Table 5 it becomes clear that the type and amount of oxidant used is very important, and oxidants that are too strong or too dark will rapidly destroy the conductive pattern. If the oxidizer is too weak or too diluted, almost nothing will happen. As can be seen from Table 5, the amount and type of halide ions are important.

Restoration of PEDOT / PSS conductivity after IPD plus treatment by reoxidation of PEDOT / PSS layer The surface resistance of the outermost PEDOT / PSS layer in material B is substantial after 30 seconds of contact with Agfa-Gebert IPD plus developer The surface resistance of the PEDOT / PSS layer of the Agfa-Gebert ^™ ORGACON film increased from 500 Ω / square to ˜3000 Ω / square in contact with it for 30 seconds. However, it has been found that the original surface resistance can be greatly improved by treatment at 25 ° C. for 30 seconds with a specific oxidant solution. The composition of the oxidant solution used and the surface resistance results obtained before contact with the IPD plus developer, after contact with the IPD plus developer, and after subsequent contact with the specific oxidant are shown in Table 6. Has been.

Best results are obtained with aqueous solutions of Na ₂ S ₂ O ₈ and FeCl ₃ , which reduce the surface resistance after contact with IPD plus developer by a factor of 2 to 1500 Ω / square, Nevertheless, it was a factor of 3 higher than the surface resistance of the organcon film before contact with the IPD plus developer.
Example 3
Conductive Ag-pattern produced by diffusion transfer reaction with patterned conductive PEDOT / PSS on top Sometimes it is necessary to have a transparent conductive layer patterned on top of a highly conductive metal pattern (For example, Example 5). This can be done by applying patterned PEDOT / PSS to the top of the emulsion layer before exposure and development (as described in Example 1) or by applying patterned PEDOT / PSS before exposure and development. This can be done by applying to the top of the layer (as described in Example 2). Similarly, patterned PEDOT / PSS can also be applied after generation of the Ag-pattern, as described in Examples 1 and 2 (Comparative). Does the patterning of PEDOT / PSS be reduced by destroying its conductivity (eg EP 1054414, EP 1079397) or flexographic printing, screen printing, tampon printing Can be increased by using printing techniques such as offset printing and ink jet printing.
Production of material G, the control material:
To 1000 mL of the above PdS dispersion was added a 50 g / L aqueous solution of Antarox CO630 from 10 mL GAF. This dispersion was then coated onto a PET substrate with a 2 μm thick gelatin subbing layer to a wet layer thickness of 13.5 μm and then dried at 25 ° C. for 60 minutes to give Material G.
Production of PEDOT / PSS Screen Printing Paste 3.47 kg 1,2-propanediol and 0.38 kg diethylene glycol in a reactor with 2.56 kg 1: 2.4 PEDOT / PSS weight ratio PEDOT / PSS In addition to the 1.2 wt.% Dispersion of PSS, 1.5 L of 1.5 L was then heated by heating using a 62 ° C. oil bath under reduced pressure varying between 31 and 55 mbar with stirring for a period of 234 minutes. The water is distilled off and the resulting mixture is cooled to 20 ° C. and then heated with stirring using a 60.5 ° C. oil bath under a reduced pressure varying between 24 and 16 mbar for a period of 287 minutes. A screen printing paste was produced by further distilling off 0.49 L of water. The water content in the 3.8 kg produced paste was 3.9% by weight as measured by the Karl Fischer method.

297 g of the resulting paste is mixed with 1.5 g of 2-glycidoxypropyl-trimethoxysilane, 0.75 g of Zonyl ^TM FSO (Zonyl ^TM FSO is a mixture of 50 wt% water and 50 wt% ethylene glycol Zonyl ^™ FSO100, 50% by weight solution) and 0.75 g of silicone antifoam agent X50860A were added to give a screen printing paste.
Production of material H:
The screen printing paste was silkscreen printed onto material G using a manual press and a P120 screen to coat the final image shown in FIG.
Exposure and development of materials G and H:
The transfer emulsion layer is exposed image-wise as shown in FIG. 1 and contacted with the receiver (Material G and Material H) using Agfa-Gebert ^™ CP297 developer solution at 25 ° C. for 10 seconds. Processed.
Production of a double-layer electrode configuration of material I:
A screen printing paste was silk screen printed onto material G processed using a manual press and a P120 screen to coat the final image shown in FIG.
Evaluation of materials G, H and I:
Table 7 shows the surface resistance and optical density (finished material) after exposure and development according to the pattern of FIG.

The results in Table 7 show that it is feasible to construct a double layer electrode by this method, but the surface resistance of the PEDOT / PSS screen printing paste was adversely affected by the Agfa-Gebert ^TM CP297 developer solution, and the surface resistance was 1500 Ω / It shows an increase from square to 18000 Ω / square.
Example 4
Conductive PEDOT / PSS with conductive Ag-pattern produced by diffusion transfer reaction on top
Production of material J as control material:
A polyethylene terephthalate support with a 4 μm gelatin subbing layer was coated to a wet thickness of 40 μm using the PEDOT / PSS dispersion described above and then dried at 100 ° C. for 15 minutes, thereby producing Material J.
Production of material K:
To 1000 mL of the above PdS dispersion was added 10 g of a 10 g / L aqueous solution of Aerosol OT from American Cyanamide and 5 g of a 50 g / L solution of perfluorocaprylamide polyglycol. This dispersion was then coated onto Material J with a wet layer thickness of 13.5 μm and then dried at 25 ° C. for 60 minutes. This material is material K.
Material K exposure and development:
The transfer emulsion layer was image-wise exposed as shown in FIG. 1 and processed with Agfa-Gebert ^™ CP297 developer solution at 25 ° C. for 10 seconds in contact with the receiver (Material K). Table 8 shows the surface resistance and optical density (finished material) after exposure and development according to the pattern of FIG.

  Table 8 shows the feasibility of a double layer electrode configuration with an Ag-conductive pattern on top of the conductive PEDOT / PSS-layer. The measured value of the surface resistance of the untreated material K is 5000 Ω / square instead of 500 Ω / square. It is not> 20 MΩ / square. This indicates a slight layer mixing and / or non-uniformity within the PdS-layer. From the above description, it is clear that the method of patterning the nuclear layer can also be applied.

Example 5
Application of patterned conductive PEDOT / PSS coated conductive Ag-pattern in the manufacture of thin film solar cells Figure 2 shows a single photovoltaic cell, two serially connected photovoltaic cells and three serially connected cells FIG. 2 shows a side (upper) and top (lower) view of a continuous process for assembling a module with an isolated photovoltaic cell using a six-stage process, where A = primed support;
B = gelatin layer,
C = palladium sulfide nucleation layer,
D = conductive silver pattern,
E = highly conductive PEDOT / PSS-layer;
F = shunt resistance blocking layer,
G = photovoltaic formulation,
H = lithium fluoride / aluminum electrode.

  In stage 1, the primed surface of the poly (ethylene terephthalate) film A [undercoat layer indicated by thin parallel lines] is coated with gelatin layer B, and in stage 2, the palladium sulfide nucleation layer C is gelatin layer B. In step 3, a diffusion transfer process is performed in which a conductive silver pattern D is produced, and in step 4, the conductive silver pattern D is high-conducting PEDOT / PSS-layer, for example by screen printing, and possibly higher Further coated with a shunt resistance blocking layer F having surface resistance, such as PEDOT / PSS layer or PEDOT-S / polycation or polyanionic polymer, and in step 5 layer E or F is for example curtain coating, spin coating or screen printing Photovoltaic formulations such as HDMO-PPV / P Formulation of BM G, in the coating and the layer G In step 6 is coated with a non-continuous lithium fluoride / aluminum layer, to produce a top electrode H.

This figure shows the use of a multilayer construction in the structure of a thin film solar cell module, for example a solar cell based on the bulk heterojunction principle. By using the method described in Example 2, a double layer electrode (Ag-pattern-PEDOT / PSS) can be constructed. As a result, charges are collected in the conductive Ag-network structure, so that a battery configuration having a larger area can be realized.
Example 6
A conceptual experiment was conducted using a recorder film having a gelatin to silver ratio of 0.014. The exposed area of 1 × 3 cm ² as an electrode with a 40 μm separation gave a conductive silver pattern by processing with conventional graphic processing. The resulting electrode pattern had a surface resistance of 50-100 ohms / square.

  The electrodes were conditioned for 3 days at 35 ° C. and 80% relative humidity. Table 9 lists the aqueous solutions used to treat the electrodes before applying a 100 V potential between adjacent electrodes.

  After treatment of the electrodes by immersion in solution at 25 ° C. for 1 minute, a potential of 100 V was applied between adjacent electrodes for 20 minutes. The results were observed under a microscope and photographed. The gap between the electrodes without pretreatment and before applying the potential was measured to be 43.0 ± 0.7 μm. Tables 10 and 11 show the final gap width and specific pretreatment and subsequent silver resin after application of 100 V potential over 20 minutes for comparative experiments using STAB01-STAB09 and experiments of the present invention using PMT01-PMT14, respectively. General observations regarding the formation of glassy crystals are recorded.

  These results show the migration of silver ions upon conditioning at 35 ° C. and 80% relative humidity for 3 days and subsequent application of a 100 V DC potential for 20 minutes without pretreatment (Comparative Experiments 2 and 3). A comparison of the results for Comparative Experiments 1 and 2 shows that conditioning clearly promoted silver resinous crystal growth as observed in the actual apparatus.

  Pretreatment with an aqueous solution of sodium tartrate (STAB02) gave limited inhibition as shown by the reduced growth of the silver resinous crystal front. Pretreatment with high concentration sodium sulfide (STAB04) seemed to peel the silver resinous crystal front from the electrode. Low concentrations of 5-methyl-s-triazolo [1,5-a] pyrimidin-7-ol (STAB05) also grow silver resinous crystals as evidenced by decomposition of the silver resinous crystal front into silver resinous groups. This was limited to a specific area.

With the notable exception of unsubstituted 1-phenyl-5-mercapto-tetrazole [STAB01], all tested 5-mercapto-tetrazoles are at least the appearance of a destroyed front formed by silver resinous crystals. As can be seen, at least limited suppression was also given to the silver resinous crystal forming step. 1-Phenyl-5-mercapto-tetrazole itself showed this performance in the presence of the surfactant, Antarox ^™ CO630, a nonionic surfactant. However, in 1-phenyl-5-mercapto-tetrazole compounds having a phenyl group substituted with at least one electron-accepting group, such as a halide, acylamino- or amide-group, as represented by compounds PMT01-PMT14, Only conspicuous suppression was observed. Nearly complete inhibition was observed with pretreatment using solutions 29, 30, 31, 39, 43, 44, 46, 51, 54 and 60, ie with pretreatment using PMT1, PMT05, PMT06, PMT08, PMT09 and PMT12. Nearly complete inhibition was observed at concentrations of 0.005% or lower of 1-phenyl-5-mercapto-tetrazole having a phenyl group substituted with an electron accepting group.

Poly (ethylene terephthalate) support with and without PMT-1 in the silver grid layer / silver grid / screen printed PEDOT-PSS-containing paste / poly {[2-methoxy-5- (2′-ethylhexoxy) -P-phenylene] vinylene}: 1- (3-methoxycarbonyl) -propyl-l-1-phenyl- (6,6) C ₆₁ layer / aluminum experiments using a halogen lamp Sometimes the results shown in Table 12 were given.

The results in Table 12 show that reduced the short circuit current presence of the silver grid from 0.7 mA / from cm ² was increased to 3.8 mA / cm ² and the open circuit voltage 830 to 740V. In addition, the introduction of PMT-1 into the silver grid layer further increased the short circuit current (I _SC ) to 5.2 mA / cm ² .

  The invention may encompass any general matter whether or not related to any feature or combination of features explicitly or explicitly disclosed herein or whether it relates to the claimed invention. . In view of the foregoing description it will be evident to a person skilled in the art that various modifications may be made within the scope of the invention.

FIG. 1 shows four silver patterns, namely a pattern (a) representing a continuous silver layer with an area of 3 × 3 cm 2, a pattern representing a regular piece pattern with parallel pieces 10 mm apart and a width of 1 mm (b) ), A pattern (c) representing a regular strip pattern with parallel strips 5 mm apart and having a width of 150 μm, and a pattern (d) representing no silver development. FIG. 2 shows the side (upper) and top (bottom) and top of a continuous process for assembling a module with a single photovoltaic cell, two series-connected photovoltaic cells and three series-connected photovoltaic cells using a six-stage method. (Bottom) shows the figure.

Claims (12)

  A method for producing a substantially transparent conductive layer configuration on a support, wherein the layer configuration comprises a first layer comprising an intrinsic conductive polymer and a second layer comprising a discontinuous layer of conductive silver. A method comprising at least any order, the method comprising producing the second layer by photographic processing.   The photographic process coats a layer containing silver halide and gelatin in a weight ratio of gelatin to silver halide in the range of 0.05 to 0.3 and exposes the silver halide-containing layer image-wise. And developing the exposed silver halide-containing layer to form the second layer.   The photographic process of claim 1, comprising coating the support with a layer of nucleation agent and using silver salt diffusion transfer to produce a discontinuous silver layer on the nucleation layer. Method.   The method of claim 3, wherein the nucleating agent is palladium sulfide. The intrinsically conductive polymer has the formula (I):

[Wherein n is greater than ¹ and each of R ¹ and R ² independently represents hydrogen or an optionally substituted C _1-4 alkyl group, or together is optionally substituted An optionally substituted C _1-4 alkylene group or an optionally substituted cycloalkylene group, preferably an ethylene group, optionally an alkyl-substituted methylene group, optionally a C _1-12 alkyl- or phenyl -Represents an optionally substituted ethylene group, 1,3-propylene group or 1,2-cyclohexylene group]
The method according to claim 1, comprising a structural unit represented by:   The method of claim 1, wherein the method further comprises coating the first layer before producing the second layer by photographic processing.   The method of claim 1, further comprising coating the first layer on the second layer comprising a silver pattern.   A layer structure obtainable by a method for producing a substantially transparent conductive layer structure on a support, wherein the layer structure contains an intrinsic conductive polymer and a discontinuous layer of conductive silver A second layer comprising at least any order, the method comprising the step of producing the second layer by photographic processing, wherein the layer configuration comprises at least one electron with a phenyl group. A layer structure further comprising a 1-phenyl-5-mercapto-tetrazole compound substituted with an accepting group.   A light emitting diode comprising a layer configuration produced by a method for producing a substantially transparent conductive layer configuration on a support, the layer configuration comprising an intrinsically conductive polymer and a conductive layer A light emitting diode comprising a second layer comprising a non-continuous layer of silver in at least any order, the method comprising the step of producing the second layer by photographic processing.   A photovoltaic device comprising a layer configuration manufactured by a method of manufacturing a substantially transparent conductive layer configuration on a support, wherein the layer configuration contains an intrinsic conductive polymer. A photovoltaic device comprising a second layer comprising a layer and a discontinuous layer of conductive silver in at least any order, the method comprising the step of producing the second layer by photographic processing.   A transistor comprising a layer configuration produced by a method for producing a substantially transparent conductive layer configuration on a support, wherein the layer configuration contains an intrinsic conductive polymer and conductive silver A transistor comprising a second layer of non-continuous layers in at least any order, the method comprising the step of producing the second layer by photographic processing.   An electroluminescent device comprising a layer arrangement produced by a method for producing a substantially transparent conductive layer arrangement on a support, the layer arrangement comprising an intrinsically conductive polymer. An electroluminescent device comprising a first layer and a second layer comprising a discontinuous layer of conductive silver in at least any order, the method comprising the step of producing the second layer by photographic processing .

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